Heavy Marine Fuel Oil Composition

ABSTRACT

A process for reducing the environmental contaminants in a ISO 8217 compliant Feedstock Heavy Marine Fuel Oil, the process involving: mixing a quantity of the Feedstock Heavy Marine Fuel Oil with a quantity of Activating Gas mixture to give a feedstock mixture; contacting the feedstock mixture with one or more catalysts to form a Process Mixture from the feedstock mixture; separating the Product Heavy Marine Fuel Oil liquid components of the Process Mixture from the gaseous components and by-product hydrocarbon components of the Process Mixture and, discharging the Product Heavy Marine Fuel Oil. The Product Heavy Marine Fuel Oil is compliant with ISO 8217 for residual marine fuel oils and the sulfur and Specific Contaminants have concentration less than 0.5 wt %., wherein the Specific Contaminates are selected from the group consisting of: vanadium, sodium, aluminum, silicon, calcium, zinc, phosphorus, nickel, iron and combinations thereof. The Product Heavy Marine Fuel Oil can be used as or as a blending stock for an ISO 8217 compliant, IMO MARPOL Annex VI (revised) compliant low sulfur or ultralow sulfur heavy marine fuel oil.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of pending U.S. application Ser. No.16/394550, filed on 25 APR. 2019, which is a continuation of grantedU.S. application Ser. No. 16/048914, filed 30 JUL. 2018, now U.S. Pat.No. 10,308,884 issued on 4 JUN. 2019, which is a continuation of nowexpired PCT/US2018/017863, filed on 12 FEB. 2018, which claims thebenefit of now expired U.S. Provisional Application No. 62/589479, filed21 NOV. 2017, and which claims benefit of now expired U.S. ProvisionalApplication No. 62/458002, filed 12 FEB. 2017.

BACKGROUND

There are two marine fuel oil types, distillate based marine fuel oil,and residual based marine fuel oil. Distillate based marine fuel oil,also known as Marine Gas Oil (MGO) or Marine Diesel Oil (MDO) comprisespetroleum fractions separated from crude oil in a refinery via adistillation process. Gasoil (also known as medium diesel) is apetroleum distillate intermediate in boiling range and viscosity betweenkerosene and lubricating oil containing a mixture of C10-19hydrocarbons. Gasoil is used to heat homes and is used for heavyequipment such as cranes, bulldozers, generators, bobcats, tractors andcombine harvesters. Generally maximizing gasoil recovery from residuesis the most economic use of the materials by refiners because they cancrack gas oils into valuable gasoline and distillates. Diesel oils arevery similar to gas oils with diesel containing predominantly contain amixture of C10-19 hydrocarbons, which include approximately 64%aliphatic hydrocarbons, 1-2% olefinic hydrocarbons, and 35% aromatichydrocarbons. Marine Diesels may contain up to 15% residual processstreams, and optionally up to no more than 5% volume of polycyclicaromatic hydrocarbons (asphaltenes). Diesel fuels are primarily utilizedas a land transport fuel and as blending component with kerosene to formaviation jet fuel.

Residual based fuels oils or Heavy Marine Fuel Oil (HMFO) comprises amixture of process residues—the fractions that don't boil or vaporizeeven under vacuum conditions, and have an asphaltene content between 3and 20 percent by weight (% wt.). Asphaltenes are large and complexpolycyclic hydrocarbons with a propensity to form complex and waxyprecipitates. Once asphaltenes have precipitated out, they arenotoriously difficult to re-dissolve and are described as fuel tanksludge in the marine shipping industry and marine bunker fuelingindustry.

Large ocean-going ships have relied upon HMFO to power large two strokediesel engines for over 50 years. HMFO is a blend of aromatics,distillates, and residues generated in the crude oil refinery process.Typical streams included in the formulation of HMFO include: atmospherictower bottoms (i.e. atmospheric residues), vacuum tower bottoms (i.e.vacuum residues) visbreaker residue, FCC Light Cycle Oil (LCO), FCCHeavy Cycle Oil (HCO) also known as FCC bottoms, FCC Slurry Oil, heavygas oils and delayed cracker oil (DCO), polycylic aromatic hydrocarbons,reclaimed land transport motor oils and small portions (less than 20% byvolume) of cutter oil, kerosene or diesel to achieve a desiredviscosity. HMFO has an aromatic content higher than the marinedistillate fuels noted above. The HMFO composition is complex and varieswith the source of crude oil and the refinery processes utilized toextract the most value out of a barrel of crude oil. The mixture ofcomponents is generally characterized as being viscous, high in sulfurand metal content, and high in asphaltenes making HMFO the one productof the refining process that has a per barrel value less than thefeedstock crude oil itself.

Industry statistics indicate that about 90% of the HMFO sold contains3.5 weight % sulfur. With an estimated total worldwide consumption ofHMFO of approximately 300 million tons per year, the annual productionof sulfur dioxide by the shipping industry is estimated to be over 21million tons per year. Emissions from HMFO burning in ships contributesignificantly to both global air pollution and local air pollutionlevels.

MARPOL, the International Convention for the Prevention of Pollutionfrom Ships, as administered by the International Maritime Organization(IMO) was enacted to prevent pollution from ships. In 1997, a new annexwas added to MARPOL; the Regulations for the Prevention of Air Pollutionfrom Ships—Annex VI to minimize airborne emissions from ships (SOx, NOx,ODS, VOC) and their contribution to air pollution. A revised Annex VIwith tightened emissions limits was adopted in October 2008 havingeffect on 1 Jul. 2010 (hereafter referred to as Annex VI (revised) orsimply Annex VI).

MARPOL Annex VI (revised) established a set of stringent emissionslimits for vessel operations in designated Emission Control Areas(ECAs). The ECAs under MARPOL Annex VI (revised) are: i) Baltic Seaarea—as defined in Annex I of MARPOL—SOx only; ii) North Sea area—asdefined in Annex V of MARPOL—SOx only; iii) North American—as defined inAppendix VII of Annex VI of MARPOL—SOx, NOx and PM; and, iv) UnitedStates Caribbean Sea area—as defined in Appendix VII of Annex VI ofMARPOL—SOx, NOx and PM.

Annex VI (revised) was codified in the United States by the Act toPrevent Pollution from Ships (APPS). Under the authority of APPS, theU.S. Environmental Protection Agency (the EPA), in consultation with theUnited States Coast Guard (USCG), promulgated regulations whichincorporate by reference the full text of MARPOL Annex VI (revised). See40 C.F.R. § 1043.100(a)(1). On Aug. 1, 2012 the maximum sulfur contentof all marine fuel oils used onboard ships operating in US waters/ECAcannot exceed 1.00% wt. (10,000 ppm) and on Jan. 1, 2015 the maximumsulfur content of all marine fuel oils used in the North American ECAwas lowered to 0.10% wt. (1,000 ppm). At the time of implementation, theUnited States government indicated that vessel operators must vigorouslyprepare for the 0.10% wt. (1,000 ppm) US ECA marine fuel oil sulfurstandard. To encourage compliance, the EPA and USCG refused to considerthe cost of compliant low sulfur fuel oil to be a valid basis forclaiming that compliant fuel oil was not available for purchase. For thepast five years there has been a very strong economic incentive to meetthe marine industry demands for low sulfur HMFO, however technicallyviable solutions have not been realized. There is an on-going and urgentdemand for processes and methods for making a low sulfur HMFO that iscompliant with MARPOL Annex VI emissions requirements.

Because of the ECAs, all ocean-going ships which operate both outsideand inside these

ECAs must operate on different marine fuel oils to comply with therespective limits and achieve maximum economic efficiency. In suchcases, prior to entry into the ECA, a ship is required to fullychange-over to using the ECA compliant marine fuel oil, and to haveonboard implemented written procedures on how this is to be undertaken.Similarly change-over from using the ECA compliant fuel oil back to HMFOis not to commence until after exiting the ECA. With each change-over itis required that the quantities of the ECA compliant fuel oils onboardare recorded, with the date, time and position of the ship when eithercompleting the change-over prior to entry or commencing change-overafter exit from such areas. These records are to be made in a logbook asprescribed by the ship's flag State, absent any specific requirement therecord could be made, for example, in the ship's Annex I Oil RecordBook.

The Annex VI (revised) also sets global limits on sulfur oxide andnitrogen oxide emissions from ship exhausts and particulate matter andprohibits deliberate emissions of ozone depleting substances, such ashydro-chlorofluorocarbons. Under the revised MARPOL Annex VI, the globalsulfur cap for HMFO was reduced to 3.50% wt. effective 1 Jan. 2012; thenfurther reduced to 0.50% wt, effective 1 Jan. 2020. This regulation hasbeen the subject of much discussion in both the marine shipping andmarine fuel bunkering industry. Under the global limit, all ships mustuse HMFO with a sulfur content of not over 0.50% wt. The IMO hasrepeatedly indicated to the marine shipping industry thatnotwithstanding availability of compliant fuel or the price of compliantfuel, compliance with the 0.50% wt. sulfur limit for HMFO will occur on1 Jan. 2020 and that the IMO expects the fuel oil market to solve thisrequirement. There has been a very strong economic incentive to meet theinternational marine industry demands for low sulfur HMFO, howevertechnically viable solutions have not been realized. There is anon-going and urgent demand for processes and methods for making a lowsulfur HMFO that is compliant with MARPOL Annex VI emissionsrequirements.

IMO Regulation 14 provides both the limit values and the means tocomply. These may be divided into methods termed primary (in which theformation of the pollutant is avoided) or secondary (in which thepollutant is formed but removed prior to discharge of the exhaust gasstream to the atmosphere). There are no guidelines regarding any primarymethods (which could encompass, for example, onboard blending of liquidfuel oils or dual fuel (gas/liquid) use). In secondary control methods,guidelines (MEPC.184(59)) have been adopted for exhaust gas cleaningsystems; in using such arrangements there would be no constraint on thesulfur content of the fuel oils as bunkered other than that given thesystem's certification. For numerous technical and economic reasons,secondary controls have been rejected by major shipping companies andnot widely adopted in the marine shipping industry. The use of secondarycontrols is not seen as practical solution by the marine shippingindustry.

Primary control solutions: A focus for compliance with the MARPOLrequirements has been on primary control solutions for reducing thesulfur levels in marine fuel components prior to combustion based on thesubstitution of HMFO with alternative fuels. However, the switch fromHMFO to alternative fuels poses a range of issues for vessel operators,many of which are still not understood by either the shipping industryor the refining industry. Because of the potential risks to shipspropulsion systems (i.e. fuel systems, engines, etc..) when a shipswitches fuel, the conversion process must be done safely andeffectively to avoid any technical issues. However, each alternativefuel has both economic and technical difficulties adapting to thedecades of shipping infrastructure and bunkering systems based upon HMFOutilized by the marine shipping industry.

LNG: The most prevalent primary control solution in the shippingindustry is the adoption of LNG as a primary or additive fuel to HMFO.An increasing number of ships are using liquified natural gas (LNG) as aprimary fuel. Natural gas as a marine fuel for combustion turbines andin diesel engines leads to negligible sulfur oxide emissions. Thebenefits of natural gas have been recognized in the development by IMOof the International Code for Ships using Gases and other Low FlashpointFuels (the IGF Code), which was adopted in 2015. LNG however presentsthe marine industry with operating challenges including: on-boardstorage of a cryogenic liquid in a marine environment will requireextensive renovation and replacement of the bunker fuel storage and fueltransfer systems of the ship; the supply of LNG is far from ubiquitousin major world ports; updated crew qualifications and training onoperating LNG or duel fuel engines will be required prior to going tosea.

Sulfur Free Bio-fuels: Another proposed primary solution for obtainingcompliance with the MARPOL requirements is the substitution of HMFO withsulfur free bio-fuels. Bio-diesel has had limited success in displacingpetroleum derived diesel however supply remains constrained. Methanolhas been used on some short sea services in the North Sea ECA on ferriesand other littoral ships. The wide spread adoption of bio-fuel, such asbio-diesel or methanol, present many challenges to ship owners and thebunker fuel industry. These challenges include: fuel systemcompatibility and adaptation of existing fuel systems will be required;contamination during long term storage of methanol and biodiesel fromwater and biological contamination; the heat content of methanol andbio-diesel on a per ton basis is substantially lower than HMFO; andmethanol has a high vapor pressure and presents serious safety concernsof flash fires.

Replacement of heavy fuel oil with marine gas oil or marine diesel: Athird proposed primary solution is to simply replace HMFO with marinegas oil (MGO) or marine diesel (MDO). The first major difficulty is theconstraint in global supply of distillate materials that make up over90% vol of MGO and MDO. It is reported that the effective spare capacityto produce MGO is less than 100 million metric tons per year resultingin an annual shortfall in marine fuel of over 200 million metric tonsper year. Refiners not only lack the capacity to increase the productionof MGO, but they have no economic motivation because higher value andhigher margins can be obtained from ultra-low sulfur diesel fuel forland-based transportation systems (i.e. trucks, trains, mass transitsystems, heavy construction equipment, etc..).

Blending: Another primary solution is the blending of HMFO with lowersulfur containing fuels such as low sulfur marine diesel (0.1% wt.sulfur) to achieve a Product HMFO with a sulfur content of 0.5% wt. In astraight blending approach (based on linear blending) every 1 ton ofHSFO (3.5% sulfur) requires 7.5 tons of MGO or MDO material with 0.1%wt. S to achieve a sulfur level of 0.5% wt. HMFO. One of skill in theart of fuel blending will immediately understand that blending hurts keyproperties of the HMFO, specifically viscosity and density aresubstantially altered. Further a blending process may result in a fuelwith variable viscosity and density that may no longer meet therequirements for a HMFO.

Further complications may arise when blended HMFO is introduced into thebunkering infrastructure and shipboard systems otherwise designed forunblended HMFO. There is a real risk of incompatibility when the twofuels are mixed. Blending a mostly paraffinic-type distillate fuel (MGOor MDO) with a HMFO having a high aromatic content often correlates withpoor solubility of asphaltenes. A blended fuel is likely to result inthe precipitation of asphaltenes and/or highly paraffinic materials fromthe distillate material forming an intractable fuel tank sludge. Fueltank sludge causes clogging of filters and separators, transfer pumpsand lines, build-up of sludge in storage tanks, sticking of fuelinjection pumps (deposits on plunger and barrel), and plugged fuelnozzles. Such a risk to the primary propulsion system is not acceptablefor a cargo ship in the open ocean.

Lastly blending of HMFO with marine distillate products (MGO or MDO) isnot economically feasible. A blender will be taking a high value product(0.1% S marine gas oil (MGO) or marine diesel (MDO)) and blending it 7.5to 1 with a low value high sulfur HMFO to create a final IMO/MARPOLcompliant HMFO (i.e. 0.5% wt. S Low Sulfur Heavy Marine FuelOil—LSHMFO). It is expected that LSHMFO will sell at a lower price on aper ton basis than the value of the two blending stocks alone.

Processing of residual oil. For the past several decades, the focus ofrefining industry research efforts related to the processing of heavyoils (crude oils, distressed oils, or residual oils) has been onupgrading the properties of these low value refinery process oils tocreate lighter oils with greater value. The challenge has been thatcrude oil, distressed oil and residues can be unstable and contain highlevels of sulfur, nitrogen, phosphorous, metals (especially vanadium andnickel) and asphaltenes. Much of the nickel and vanadium is in difficultto remove chelates with porphyrins. Vanadium and nickel porphyrins andother metal organic compounds are responsible for catalyst contaminationand corrosion problems in the refinery. The sulfur, nitrogen, andphosphorous, are removed because they are well-known poisons for theprecious metal (platinum and palladium) catalysts utilized in theprocesses downstream of the atmospheric or vacuum distillation towers.

The difficulties treating atmospheric or vacuum residual streams hasbeen known for many years and has been the subject of considerableresearch and investigation. Numerous residue-oil conversion processeshave been developed in which the goals are same, 1) create a morevaluable, preferably distillate range hydrocarbon product; and 2)concentrate the contaminates such as sulfur, nitrogen, phosphorous,metals and asphaltenes into a form (coke, heavy coker residue, FCCslurry oil) for removal from the refinery stream. Well known andaccepted practice in the refining industry is to increase the reactionseverity (elevated temperature and pressure) to produce hydrocarbonproducts that are lighter and more purified, increase catalyst lifetimes and remove sulfur, nitrogen, phosphorous, metals and asphaltenesfrom the refinery stream.

It is also well known in these processes that the nature of thefeedstock has a significant influence upon the products produced,catalyst life, and ultimately the economic viability of the process. Ina representative technical paper Residual-Oil Hydrotreating Kinetics forGraded Catalyst Systems: Effects of Original and Treated Feedstocks, isstated that “The results revealed significant changes in activity,depending on the feedstock used for the tests. The study demonstratesthe importance of proper selection of the feedstocks used in theperformance evaluation and screening of candidate catalyst for gradedcatalyst systems for residual-oil hydrotreatment.” From this one skilledin the art would understand that the conditions required for thesuccessful hydroprocessing of atmospheric residue are not applicable forthe successful hydroprocessing of vacuum residue which are notapplicable for the successful hydroprocessing of a visbreaker residue,and so forth. Successful reaction conditions depend upon the feedstock.For this reason modern complex refineries have multiple hydroprocessingunits, each unit being targeted on specific hydrocarbon stream with afocus on creating desirable and valuable light hydrocarbons andproviding a product acceptable to the next downstream process.

A further difficulty in the processing of heavy oil residues and otherheavy hydrocarbons is the inherent instability of each intermediaterefinery stream. One of skill in the art understands there are manypractical reasons each refinery stream is handled in isolation. One suchreason is the unpredictable nature of the asphaltenes contained in eachstream. Asphaltenes are large and complex hydrocarbons with a propensityto precipitate out of refinery hydrocarbon streams. One of skill in theart knows that even small changes in the components or physicalconditions (temperature, pressure) can precipitate asphaltenes that wereotherwise dissolved in solution. Once precipitated from solution,asphaltenes can quickly block vital lines, control valves, coat criticalsensing devices (i.e. temperature and pressure sensors) and generallyresult in the severe and very costly disruption and shut down of a unitor the whole refinery. For this reason it has been a long-standingpractice within refineries to not blend intermediate product streams(such as atmospheric residue, vacuum residue, FCC slurry oil, etc...)and process each stream in separate reactors.

In summary, since the announcement of the MARPOL standards reducing theglobal levels of sulfur in HMFO, refiners of crude oil have notundertaken the technical efforts to create a low sulfur substitute forHMFO. Despite the strong governmental and economic incentives and needsof the international marine shipping industry, refiners have littleeconomic reason to address the removal of environmental contaminatesfrom HMFOs. Instead the global refining industry has been focused upongenerating greater value from each barrel of oil by creating lighthydrocarbons (i.e. diesel and gasoline) and concentrating theenvironmental contaminates into increasingly lower value streams (i.e.residues) and products (petroleum coke, HMFO). Shipping companies havefocused on short term solutions, such as the installation of scrubbingunits, or adopting the limited use of more expensive low sulfur marinediesel and marine gas oils as a substitute for HMFO. On the open seas,most if not all major shipping companies continue to utilize the mosteconomically viable fuel, that is HMFO. There remains a long standingand unmet need for processes and devices that remove the environmentalcontaminants (i.e. sulfur, nitrogen, phosphorous, metals especiallyvanadium and nickel) from HMFO without altering the qualities andproperties that make HMFO the most economic and practical means ofpowering ocean going vessels. Further there remains a long standing andunmet need for IMO compliant low sulfur (i.e. 0.5% wt. sulfur) orultralow (0.10% wt. sulfur) HMFO that is also compliant with the bulkproperties required for a merchantable ISO 8217 HMFO.

SUMMARY

It is a general objective to reduce the environmental contaminates froma Heavy Marine

Fuel Oil (HMFO) in a process that minimizes the changes in the desirableproperties of the HMFO and minimizes the unnecessary production ofby-product hydrocarbons (i.e. light hydrocarbons (C₁-C₈) and wildnaphtha (C₅-C₂₀).

A first aspect and illustrative embodiment encompasses a process forreducing the environmental contaminants in a Feedstock Heavy Marine FuelOil, the process involving: mixing a quantity of Feedstock Heavy MarineFuel Oil with a quantity of Activating Gas mixture to give a FeedstockMixture; contacting the Feedstock Mixture with one or more catalysts toform a Process Mixture from the Feedstock Mixture; receiving saidProcess Mixture and separating a Product Heavy Marine Fuel Oil liquidcomponents of the Process Mixture from the gaseous components andby-product hydrocarbon components of the Process Mixture and,discharging the Product Heavy Marine Fuel Oil.

A second aspect and illustrative embodiment encompasses a hydrocarbonfuel composition, referred to herein as a Heavy Marine Fuel Composition,consisting essentially of at least a majority by volume, preferably 85%by volume, more preferably at least 90% by volume and most preferably atleast 95% by volume of the Product Heavy Marine Fuel Oil resulting fromthe disclosed process for reducing the environmental contaminants in aFeedstock Heavy Marine Fuel Oil or optionally produced by devicesembodying that process. The balance of the volume in the Heavy MarineFuel Composition may be Diluent Materials with the Product HMFO but donot result in a mixture that fails to comply with the ISO 8217 :2017standards for the bulk properties of residual marine fuels and achievesa sulfur content lower than the global MARPOL standard of 0.5% wt.sulfur (ISO 14596 or ISO 8754).

A third aspect and illustrative embodiment encompasses a device forreducing environmental contaminants in a Feedstock HMFO and producing aProduct HMFO. The illustrative device comprises a first vessel, a secondvessel in fluid communication with the first vessel and a third vesselin fluid communication with the second vessel and a discharge line fromthe third vessel for discharging the Product HMFO. The first vesselreceives a quantity of the Feedstock HMFO mixed with a quantity of anActivating Gas mixture and contacting the resulting mixture with one ormore catalysts under certain process conditions to form a ProcessMixture. The second vessel receives the Process Mixture from the firstvessel, separates the liquid components from the bulk gaseous componentswithin the Process Mixture. The bulk gaseous components are sent on forfurther processing. The liquid components are sent to the third vesselseparates any residual gaseous component and any by-product hydrocarboncomponents (principally lights and wild naphtha) from the processedProduct HMFO which is subsequently discharged.

DESCRIPTION OF DRAWINGS

FIG. 1 is a process flow diagram of a process to produce Product HMFO.

FIG. 2 is a basic schematic diagram of a plant to produce Product HMFO.

DETAILED DESCRIPTION

The inventive concepts as described herein utilize terms that should bewell known to one of skill in the art, however certain terms areutilized having a specific intended meaning and these terms are definedbelow:

Heavy Marine Fuel Oil (HMFO) is a petroleum product fuel compliant withthe ISO 8217 :2017 standards for the bulk properties of residual marinefuels except for the concentration levels of the EnvironmentalContaminates.

Environmental Contaminates are organic and inorganic components of HMFOthat result in the formation of SO_(x), NO_(x) and particulate materialsupon combustion.

Feedstock HMFO is a petroleum product fuel compliant with the ISO 8217:2017 standards for the bulk properties of residual marine fuels exceptfor the concentration of Environmental Contaminates, preferably theFeedstock HMFO has a sulfur content greater than the global MARPOLstandard of 0.5% wt. sulfur, and preferably and has a sulfur content(ISO 14596 or ISO 8754) between the range of 5.0% wt. to 1.0% wt. .

Heavy Marine Fuel Composition is a hydrocarbon fuel compositionconsisting essentially of at least 85% by volume of the Product HMFO andno more than 15% by volume of Diluent Materials and complies with theISO 8217 :2017 standards for the bulk properties of residual marinefuels and a sulfur content lower than the global MARPOL standard of 0.5%wt. sulfur (ISO 14596 or ISO 8754).

Diluent Materials are hydrocarbon or non-hydrocarbon materials mixedinto or combined with or added to and solids suspended in the ProductHMFO, the presence of which does not result in a mixture that fails tocomply with the ISO 8217 :2017 standards for the bulk properties ofresidual marine fuels and result in a sulfur content greater than theglobal MARPOL standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754).

Product HMFO is a petroleum product fuel compliant with the ISO 8217:2017 standards for the bulk properties of residual marine fuels andachieves a sulfur content lower than the global MARPOL standard of 0.5%wt. sulfur (ISO 14596 or ISO 8754), and preferably a maximum sulfurcontent (ISO 14596 or ISO 8754) between the range of 0.05% wt. to 1.0%wt.

Activating Gas: is a mixture of gases utilized in the process combinedwith the catalyst to remove the environmental contaminates from theFeedstock HMFO.

Fluid communication: is the capability to transfer fluids (eitherliquid, gas or combinations thereof, which might have suspended solids)from a first vessel or location to a second vessel or location, this mayencompass connections made by pipes (also called a line), spools,valves, intermediate holding tanks or surge tanks (also called a drum).

Merchantable quality: is a level of quality for a residual marine fueloil so that the fuel is fit for the ordinary purpose it is intended toserve (i.e. serve as a residual fuel source for a marine ship) and canbe commercially sold as and is fungible with heavy or residual marinebunker fuel.

Bbl or bbl: is a standard volumetric measure for oil; 1 bbl=0.1589873m³; or 1 bbl=158.9873 liters; or 1 bbl=42.00 US liquid gallons.

Bpd: is an abbreviation for Bbl per day.

SCF: is an abbreviation for standard cubic foot of a gas; a standardcubic foot (at 14.73 psi and 60° F.) equals 0.0283058557 standard cubicmeters (at 101.325 kPa and 15° C.).

The inventive concepts are illustrated in more detail in thisdescription referring to the drawings, in which FIG. 1 shows thegeneralized block process flows for reducing the environmentalcontaminates in a Feedstock HMFO and producing a Product HMFO accordingto a first illustrative embodiment. A predetermined volume of FeedstockHMFO (2) is mixed with a predetermined quantity of Activating Gas (4) togive a Feedstock Mixture. The Feedstock HMFO utilized generally complieswith the bulk physical and certain key chemical properties for aresidual marine fuel oil otherwise compliant with ISO8217:2017 exclusiveof the Environmental Contaminates. More particularly, when theEnvironmental Contaminate is sulfur, the concentration of sulfur in theFeedstock HMFO may be between the range of 5.0% wt. to 1.0% wt. TheFeedstock HMFO should have bulk physical properties that are required ofan ISO8217:2017 compliant HMFO of: a maximum kinematic viscosity at 50 °C. (ISO 3104) between the range from 180 mm²/s to 700 mm²/s and amaximum density at 15° C. (ISO 3675) between the range of 991.0 kg/m³ to1010.0 kg/m³ and a CCAI is 780 to 870 and a flash point (ISO 2719) nolower than 60.0° C. Other properties of the Feedstock HMFO connected tothe formation of particulate material (PM) include: a maximum totalsediment—aged (ISO 10307-2) of 0.10% wt. and a maximum carbonresidue—micro method (ISO 10370) between the range of 18.00% wt. and20.00% wt. and a maximum aluminum plus silicon (ISO 10478) content of 60mg/kg. Potential Environmental Contaminates other than sulfur that maybe present in the Feedstock HMFO over the ISO requirements may includevanadium, nickel, iron, aluminum and silicon substantially reduced bythe process of the present invention. However, one of skill in the artwill appreciate that the vanadium content serves as a general indicatorof these other Environmental Contaminates. In one preferred embodimentthe vanadium content is ISO compliant so the Feedstock MHFO has amaximum vanadium content (ISO 14597) between the range from 350 mg/kg to450 ppm mg/kg.

As for the properties of the Activating Gas, the Activating Gas shouldbe selected from mixtures of nitrogen, hydrogen, carbon dioxide, gaseouswater, and methane. The mixture of gases within the Activating Gasshould have an ideal gas partial pressure of hydrogen (p_(H2)) greaterthan 80% of the total pressure of the Activating Gas mixture (P) andmore preferably wherein the Activating Gas has an ideal gas partialpressure of hydrogen (p_(H2)) greater than 95% of the total pressure ofthe Activating Gas mixture (P). It will be appreciated by one of skillin the art that the molar content of the Activating Gas is anothercriteria the Activating Gas should have a hydrogen mole fraction in therange between 80% and 100% of the total moles of Activating Gas mixture,more preferably wherein the Activating Gas has a hydrogen mole fractionbetween 80% and 99% of the total moles of Activating Gas mixture

The Feedstock Mixture (i.e. mixture of Feedstock HMFO and ActivatingGas) is brought up to the process conditions of temperature and pressureand introduced into a first vessel, preferably a reactor vessel, so theFeedstock Mixture is then contacted with one or more catalysts (8) toform a Process Mixture from the Feedstock Mixture.

The process conditions are selected so the ratio of the quantity of theActivating Gas to the quantity of Feedstock HMFO is 250 scf gas/bbl ofFeedstock HMFO to 10,000 scf gas/bbl of Feedstock HMFO; and preferablybetween 2000 scf gas/bbl of Feedstock HMFO; 1 to 5000 scf gas/bbl ofFeedstock HMFO more preferably between 2500 scf gas/bbl of FeedstockHMFO to 4500 scf gas/bbl of Feedstock HMFO. The process conditions areselected so the total pressure in the first vessel is between of 250psig and 3000 psig; preferably between 1000 psig and 2500 psig, and morepreferably between 1500 psig and 2200 psig The process conditions areselected so the indicated temperature within the first vessel is betweenof 500° F. to 900° F., preferably between 650° F. and 850° F. and morepreferably between 680° F. and 800° F. The process conditions areselected so the liquid hourly space velocity within the first vessel isbetween 0.05 oil/hour/m³ catalyst and 1.0 oil/hour/m³ catalyst;preferably between 0.08 oil/hour/m³ catalyst and 0.5 oil/hour/m³catalyst; and more preferably between 0.1 oil/hour/m³ catalyst and 0.3oil/hour/m³ catalyst to achieve desulfurization with product sulfurlevels below 0.5% wt.

One of skill in the art will appreciate that the process conditions aredetermined to consider the hydraulic capacity of the unit. Exemplaryhydraulic capacity for the treatment unit may be between 100 bbl ofFeedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day, preferablybetween 1000 bbl of Feedstock HMFO/day and 60,000 bbl of FeedstockHMFO/day, more preferably between 5,000 bbl of Feedstock HMFO/day and45,000 bbl of Feedstock HMFO/day, and even more preferably between10,000 bbl of Feedstock HMFO/day and 30,00 bbl of Feedstock HMFO/day.

The process may utilize one or more catalyst systems selected from thegroup consisting of: an ebulliated bed supported transition metalheterogeneous catalyst, a fixed bed supported transition metalheterogeneous catalyst, and a combination of ebulliated bed supportedtransition metal heterogeneous catalysts and fixed bed supportedtransition metal heterogeneous catalysts. One of skill in the art willappreciate that a fixed bed supported transition metal heterogeneouscatalyst will be the technically easiest to implement and is preferred.The transition metal heterogeneous catalyst comprises a porous inorganicoxide catalyst carrier and a transition metal catalyst. The porousinorganic oxide catalyst carrier is at least one carrier selected fromthe group consisting of alumina, alumina/boria carrier, a carriercontaining metal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier. The transition metal component of thecatalyst is one or more metals selected from the group consisting ofgroup 6, 8, 9 and 10 of the Periodic Table. In a preferred andillustrative embodiment, the transition metal heterogeneous catalyst isa porous inorganic oxide catalyst carrier and a transition metalcatalyst, in which the preferred porous inorganic oxide catalyst carrieris alumina and the preferred transition metal catalyst is Ni—Mo, Co—Mo,Ni—W or Ni—Co—Mo

The Process Mixture (10) is removed from the first vessel (8) and frombeing in contact with the one or more catalyst and is sent via fluidcommunication to a second vessel (12), preferably a gas-liquid separatoror hot separators and cold separators, for separating the liquidcomponents (14) of the Process Mixture from the bulk gaseous components(16) of the Process Mixture. The gaseous components (16) are treatedbeyond the battery limits of the immediate process. Such gaseouscomponents may include a mixture of Activating Gas components andlighter hydrocarbons (mostly methane, ethane and propane but some wildnaphtha) that may have been unavoidably formed as part of the by-producthydrocarbons from the process.

The Liquid Components (16) are sent via fluid communication to a thirdvessel (18), preferably a fuel oil product stripper system, forseparating any residual gaseous components (20) and by-producthydrocarbon components (22) from the Product HMFO (24). The residualgaseous components (20) may be a mixture of gases selected from thegroup consisting of: nitrogen, hydrogen, carbon dioxide, hydrogensulfide, gaseous water, C₁-C₅ light hydrocarbons. This residual gas istreated outside of the battery limits of the immediate process, combinedwith other gaseous components (16) removed from the Process Mixture (10)in the second vessel (12). The liquid by-product hydrocarbon component,which are condensable hydrocarbons unavoidably formed in the process(22) may be a mixture selected from the group consisting of C₅-C₂₀hydrocarbons (wild naphtha) (naphtha—diesel) and other condensable lightliquid (C₄-C₈) hydrocarbons that can be utilized as part of the motorfuel blending pool or sold as gasoline and diesel blending components onthe open market.

As a side note, the residual gaseous component is a mixture of gasesselected from the group consisting of: nitrogen, hydrogen, carbondioxide, hydrogen sulfide, gaseous water, light hydrocarbons. An aminescrubber will effectively remove the hydrogen sulfide content which canthen be processed using technologies and processes well known to one ofskill in the art. In one preferable illustrative embodiment, thehydrogen sulfide is converted into elemental sulfur using the well-knownClaus process. An alternative embodiment utilizes a proprietary processfor conversion of the Hydrogen sulfide to hydro sulfuric acid. Eitherway, the sulfur is removed from entering the environment prior tocombusting the HMFO in a ships engine. The cleaned gas can be vented,flared or more preferably recycled back for use as Activating Gas.

The by-product hydrocarbon components are a mixture of C₅-C₂₀hydrocarbons (wild naphtha) (naphtha—diesel) which can be directed tothe motor fuel blending pool or sold over the fence to an adjoiningrefinery or even utilized to fire the heaters and combustion turbines toprovide heat and power to the process. These by product hydrocarbonswhich are the result of hydrocracking reactions should be less than 10%wt. , preferably less than 5% wt. and more preferably less than 2% wt.of the overall process mass balance.

The Product HMFO (24) is discharged via fluid communication into storagetanks beyond the battery limits of the immediate process.

Product HMFO The Product HFMO resulting from the disclosed illustrativeprocess is of merchantable quality for sale and use as a heavy marinefuel oil (also known as a residual marine fuel oil or heavy bunker fuel)and exhibits the bulk physical properties required for the Product HMFOto be an ISO compliant (i.e. ISO8217:2017) residual marine fuel oilexhibiting the bulk properties of: a maximum kinematic viscosity at 50C(ISO 3104) between the range from 180 mm²/s to 700 mm²/s; a maximumdensity at 15° C. (ISO 3675) between the range of 991.0 kg/m³ to 1010.0kg/m³; a CCAI is in the range of 780 to 870; a flash point (ISO 2719) nolower than 60.0° C. a maximum total sediment—aged (ISO 10307-2) of 0.10%wt. ; a maximum carbon residue—micro method (ISO 10370) between therange of 18.00% wt. and 20.00% wt. , and a maximum aluminum plus silicon(ISO 10478) content of 60 mg/kg.

The Product HMFO has a sulfur content (ISO 14596 or ISO 8754) less than0.5% wt. and preferably less than 0.1% wt. and more preferably less than0.05% wt. and is fully compliant with the IMO Annex VI (revised)requirements for a low sulfur and preferably an ultra-low sulfur HMFO.That is the sulfur content of the Product HMFO has been reduced by about90% or greater when compared to the Feedstock HMFO. Similarly, thevanadium content (ISO 14597) of the Product Heavy Marine Fuel Oil isless than 10% and more preferably less than 1% of the maximum vanadiumcontent of the Feedstock Heavy Marine Fuel Oil. One of skill in the artwill appreciate that a substantial reduction in sulfur and vanadiumcontent of the Feedstock HMFO indicates a process having achieved asubstantial reduction in the Environmental Contaminates from theFeedstock HMFO; of equal importance is that this has been achieved whilemaintaining the desirable properties of an ISO8217:2017 compliant HMFO.

The Product HMFO not only complies with ISO8217:2017 (and ismerchantable as a residual marine fuel oil or bunker fuel), the ProductHMFO has a maximum sulfur content (ISO 14596 or ISO 8754) between therange of 0.05% wt. to 1.0% wt. preferably a sulfur content (ISO 14596 orISO 8754) between the range of 0.05% wt. ppm and 0.5% wt. and morepreferably a sulfur content (ISO 14596 or ISO 8754) between the range of0.1% wt. and 0.05% wt. The vanadium content of the Product HMFO is wellwithin the maximum vanadium content (ISO 14597) required for anISO8217:2017 residual marine fuel oil exhibiting a vanadium contentlower than 450 ppm mg/kg, preferably a vanadium content (ISO 14597)lower than 300 mg/kg and more preferably a vanadium content (ISO 14597)between the range of 50 mg/kg and 100 mg/kg.

One knowledgeable in the art of marine fuel blending, bunker fuelformulations and the fuel logistical requirements for marine shippingfuels will readily appreciate that without further compositional changesor blending, the Product HMFO can be sold and used as a low sulfurMARPOL Annex VI compliant heavy (residual) marine fuel oil that is adirect substitute for the high sulfur heavy (residual) marine fuel oilor heavy bunker fuel currently in use. One illustrative embodiment is anISO8217:2017 compliant low sulfur heavy marine fuel oil comprising (andpreferably consisting essentially of) a 100% hydroprocessed ISO8217:2017compliant high sulfur heavy marine fuel oil, wherein the sulfur levelsof the hydroprocessed ISO8217:2017 compliant high sulfur heavy marinefuel oil is greater than 0.5% wt. and wherein the sulfur levels of theISO8217:2017 compliant low sulfur heavy marine fuel oil is less than0.5% wt. Another illustrative embodiment is an ISO8217:2017 compliantultra-low sulfur heavy marine fuel oil comprising (and preferablyconsisting essentially of) a 100% hydroprocessed ISO8217:2017 complianthigh sulfur heavy marine fuel oil, wherein the sulfur levels of thehydroprocessed ISO8217:2017 compliant high sulfur heavy marine fuel oilis greater than 0.5% wt. and wherein the sulfur levels of theISO8217:2017 compliant low sulfur heavy marine fuel oil is less than0.1% wt.

As a result of the present invention, multiple economic and logisticalbenefits to the bunkering and marine shipping industries can berealized. More specifically the benefits include minimal changes to theexisting heavy marine fuel bunkering infrastructure (storage andtransferring systems); minimal changes to shipboard systems are neededto comply with emissions requirements of MARPOL Annex VI (revised); noadditional training or certifications for crew members will be needed,amongst the realizable benefits. Refiners will also realize multipleeconomic and logistical benefits, including: no need to alter orrebalance the refinery operations and product streams to meet a newmarket demand for low sulfur or ultralow sulfur HMFO; no additionalunits are needed in the refinery along with accompanying additionalhydrogen or sulfur capacity because the illustrative process can beconducted as a stand-alone unit; refinery operations can remain focusedon those products that create the greatest value from the crude oilreceived (i.e. production of petrochemicals, gasoline and distillate(diesel); refiners can continue using the existing slates of crude oilswithout having to switch to sweeter or lighter crudes to meet theenvironmental requirements for HMFO products; to name a few.

Heavy Marine Fuel Composition One aspect of the present inventiveconcept is a fuel composition comprising, but preferably consistingessentially of, the Product HMFO resulting from the processes disclosed,and may optionally include Diluent Materials. As noted above, the bulkproperties of the Product HMFO itself complies with ISO8217:2017 andmeets the global IMO Annex VI requirements for maximum sulfur content(ISO 14596 or ISO 8754). To the extent that ultra-low levels of sulfurare desired, the process of the present invention achieves this and oneof skill in the art of marine fuel blending will appreciate that a lowsulfur or ultra-low sulfur Product HMFO can be utilized as a primaryblending stock to form a global IMO Annex VI compliant low sulfur HeavyMarine Fuel Composition. Such a low sulfur Heavy Marine Fuel Compositionwill comprise (and preferably consist essentially of): a) the ProductHMFO and b) Diluent Materials. In one embodiment, the majority of thevolume of the Heavy Marine Fuel Composition is the Product HMFO with thebalance of materials being Diluent Materials. Preferably, the HeavyMaine Fuel Composition is at least 75% by volume, preferably at least80% by volume, more preferably at least 90% by volume, and furthermorepreferably at least 95% by volume Product HMFO with the balance beingDiluent Materials.

Diluent Materials may be hydrocarbon or non-hydrocarbon based materialsthat are mixed into or combined with or added to, or solid particlematerials that are suspended in, the Product HMFO. The Diluent Materialsmay intentionally or unintentionally alter the composition of theProduct HMFO but not in a way that the resulting mixture fails to complywith the ISO 8217 :2017 standards for the bulk properties of residualmarine fuels or fails to have a sulfur content lower than the globalMARPOL standard of 0.5% wt. sulfur (ISO 14596 or ISO 8754). Examples ofDiluent Materials that are considered to be hydrocarbon based materialsinclude: Feedstock HMFO (i.e. high sulfur HMFO); distillate based fuelssuch as road diesel, gas oil, MGO or MDO; cutter oil (which is currentlyused in formulating residual marine fuel oils); renewable oils and fuelssuch as biodiesel, methanol, ethanol, and the like; synthetichydrocarbons and oils based on gas to liquids technology such asFischer-Tropsch derived oils, fully synthetic oils such as those basedon polyethylene, polypropylene, dimer, trimer and poly butylene and thelike; refinery residues or other hydrocarbon oils such as atmosphericresidue, vacuum residue, fluid catalytic cracker (FCC) slurry oil, FCCcycle oil, pyrolysis gasoil, cracked light gas oil (CLGO), cracked heavygas oil (CHGO), light cycle oil (LCO), heavy cycle oil (HCO), thermallycracked residue, coker heavy distillate, bitumen, de-asphalted heavyoil, visbreaker residue, slop oils, asphaltene oils; used or recycledmotor oils; lube oil aromatic extracts and crude oils such as heavycrude oil, distressed crude oils and similar materials that mightotherwise be sent to a hydrocracker or diverted into the blending poolfor a prior art high sulfur heavy (residual) marine fuel oil. Examplesof Diluent Materials that are considered to be non-hydrocarbon basedmaterials include: residual water (i.e. water that is absorbed from thehumidity in the air or water that is miscible or solubilized, in somecases as microemulsions, into the hydrocarbons of the Product HMFO),fuel additives which can include, but are not limited to detergents,viscosity modifiers, pour point depressants, lubricity modifiers,de-hazers (e.g. alkoxylated phenol formaldehyde polymers), antifoamingagents (e.g. polyether modified polysiloxanes); ignition improvers; antirust agents (e.g. succinic acid ester derivatives); corrosioninhibitors; anti-wear additives, anti-oxidants (e.g. phenolic compoundsand derivatives), coating agents and surface modifiers, metaldeactivators, static dissipating agents, ionic and nonionic surfactants,stabilizers, cosmetic colorants and odorants and mixtures of these. Athird group of Diluent Materials may include suspended solids or fineparticulate materials that are present as a result of the handling,storage and transport of the Product HMFO or the Heavy Marine FuelComposition, including but not limited to: carbon or hydrocarbon solids(e.g. coke, graphitic solids, or micro-agglomerated asphaltenes), ironrust and other oxidative corrosion solids, fine bulk metal particles,paint or surface coating particles, plastic or polymeric or elastomer orrubber particles (e.g. resulting from the degradation of gaskets, valveparts, etc...), catalyst fines, ceramic or mineral particles, sand,clay, and other earthen particles, bacteria and other biologicallygenerated solids, and mixtures of these that may be present as suspendedparticles, but otherwise don't detract from the merchantable quality ofthe Heavy Marine Fuel Composition as an ISO 8217 :2017 compliant heavy(residual) marine fuel.

The blend of Product HMFO and Diluent Materials must be of merchantablequality as a low sulfur heavy (residual) marine fuel. That is the blendmust be suitable for the intended use as heavy marine bunker fuel andgenerally be fungible as a bunker fuel for ocean going ships. Preferablythe Heavy Marine Fuel Composition must retain the bulk physicalproperties that are required of an ISO 8217 :2017 compliant residualmarine fuel oil and a sulfur content lower than the global MARPOLstandard of 0.5% wt. sulfur (ISO 14596 or ISO 8754) so that the materialqualifies as MARPOL Annex VI Low Sulfur Heavy Marine Fuel Oil (LS-HMFO).As noted above, the sulfur content of the Product HMFO can besignificantly lower than 0.5% wt. (i.e. below 0.1%wt sulfur (ISO 14596or ISO 8754)) to qualify as a MARPOL Annex VI (revised) Ultra-Low SulfurHeavy Marine Fuel Oil (ULS-HMFO) and a Heavy Marine Fuel Compositionlikewise can be formulated to qualify as a MARPOL Annex VI compliantULS-HMFO suitable for use as marine bunker fuel in the ECA zones. Toqualify as an ISO 8217 :2017 qualified fuel, the Heavy Marine FuelComposition of the present invention must meet those internationallyaccepted standards including: a maximum kinematic viscosity at 50C (ISO3104) between the range from 180 mm²/s to 700 mm²/s; a maximum densityat 15° C. (ISO 3675) between the range of 991.0 kg/m³ to 1010.0 kg/m³; aCCAI is in the range of 780 to 870; a flash point (ISO 2719) no lowerthan 60.0° C. a maximum total sediment—aged (ISO 10307-2) of 0.10% wt.;a maximum carbon residue—micro method (ISO 10370) between the range of18.00% wt. and 20.00% wt., and a maximum aluminum plus silicon (ISO10478) content of 60 mg/kg.

Production Plant Description: Turning now to a more detailedillustrative embodiment of a production plant, FIG. 2 shows a schematicfor a production plant implementing the process described above forreducing the environmental contaminates in a Feedstock HMFO to produce aProduct HMFO according to the second illustrative embodiment. Analternative embodiment for the production plant in which multiplereactors are utilized is within the scope of the present invention andis described in a co-pending disclosure.

In FIG. 2, Feedstock HMFO (A) is fed from outside the battery limits(OSBL) to the Oil Feed Surge Drum (1) that receives feed from outsidethe battery limits (OSBL) and provides surge volume adequate to ensuresmooth operation of the unit. Water entrained in the feed is removedfrom the HMFO with the water being discharged a stream (1 c) fortreatment OSBL.

The Feedstock HMFO (A) is withdrawn from the Oil Feed Surge Drum (1) vialine (lb) by the Oil Feed Pump (3) and is pressurized to a pressurerequired for the process. The pressurized HMFO (A′) then passes throughline (3 a) to the Oil Feed/Product Heat Exchanger (5) where thepressurized HMFO Feed (A′) is partially heated by the Product HMFO (B).The Product HMFO (B) is a hydrocarbon stream with sulfur content lessthan 5000 ppmw and preferably less than 1000 ppmw. Hydrocarbons in theFeedstock HMFO and Product HMFO range between C₁₂ and C₇₀₊ and theboiling range is between 350° F. and 1110+F. The pressurized FeedstockHMFO (A′) passing through line (5 a) is further heated against theeffluent from the Reactor System (E) in the Reactor Feed/Effluent HeatExchanger (7).

The heated and pressurized Feedstock HMFO (A″) in line (7 a) is thenmixed with Activating Gas (C) provided via line (23 c) at Mixing Point(X) to form a Feedstock Mixture (D). The mixing point (X) can be anywell know gas/liquid mixing system or entrainment mechanism well knownto one skilled in the art.

The Feedstock Mixture (D) passes through line (9 a) to the Reactor FeedFurnace (9) where the Feedstock Mixture (D) is heated to the specifiedprocess temperature. The Reactor Feed Furnace (9) may be a fired heaterfurnace or any other kind to type of heater as known to one of skill inthe art if it will raise the temperature of the Feedstock mixture to thedesired temperature for the process conditions.

The fully heated Feedstock Mixture (D′) exits the Reactor Feed Furnace(9) via line 9 b and is fed into the Reactor System (11). The fullyheated Feedstock Mixture (D′) enters the Reactor System (11) whereenvironmental contaminates, such a sulfur, nitrogen, and metals arepreferentially removed from the Feedstock HMFO component of the fullyheated Feedstock Mixture. The Reactor System contains a catalyst whichpreferentially removes the sulfur compounds in the Feedstock HMFOcomponent by reacting them with hydrogen in the Activating Gas to formhydrogen sulfide. The Reactor System will also achieve demetalization,denitrogenation, and a certain amount of ring opening hydrogenation ofthe complex aromatics and asphaltenes, however minimal hydrocracking ofhydrocarbons should take place. The process conditions of hydrogenpartial pressure, reaction pressure, temperature and residence time asmeasured by time space velocity are optimized to achieve desired finalproduct quality. A more detailed discussion of the Reactor System, thecatalyst, the process conditions, and other aspects of the process arecontained below in the “Reactor System Description.”

The Reactor System Effluent (E) exits the Reactor System (11) via line(11 a) and exchanges heat against the pressurized and partially heatsthe Feedstock HMFO (A′) in the Reactor Feed/Effluent Exchanger (7). Thepartially cooled Reactor System Effluent (E′) then flows via line (11 c)to the Hot Separator (13).

The Hot Separator (13) separates the gaseous components of the ReactorSystem Effluent (F) which are directed to line (13 a) from the liquidcomponents of the Reactor System effluent (G) which are directed to line(13 b). The gaseous components of the Reactor System effluent in line(13 a) are cooled against air in the Hot Separator Vapor Air Cooler (15)and then flow via line (15 a) to the Cold Separator (17).

The Cold Separator (17) further separates any remaining gaseouscomponents from the liquid components in the cooled gaseous componentsof the Reactor System Effluent (F′). The gaseous components from theCold Separator (F″) are directed to line (17 a) and fed onto the AmineAbsorber (21). The Cold Separator (17) also separates any remaining ColdSeparator hydrocarbon liquids (H) in line (17 b) from any Cold Separatorcondensed liquid water (I). The Cold Separator condensed liquid water(I) is sent OSBL via line (17 c) for treatment.

The hydrocarbon liquid components of the Reactor System effluent fromthe Hot Separator (G) in line (13 b) and the Cold Separator hydrocarbonliquids (H) in line (17 b) are combined and are fed to the Oil ProductStripper System (19). The Oil Product Stripper System (19) removes anyresidual hydrogen and hydrogen sulfide from the Product HMFO (B) whichis discharged in line (19 b) to storage OSBL. The vent stream (M) fromthe Oil Product Stripper in line (19 a) may be sent to the fuel gassystem or to the flare system that are OSBL. A more detailed discussionof the Oil Product Stripper System is contained in the “Oil ProductStripper System Description.”

The gaseous components from the Cold Separator (F″) in line (17 a)contain a mixture of hydrogen, hydrogen sulfide and light hydrocarbons(mostly methane and ethane). This vapor stream (17 a) feeds an AmineAbsorber (21) where it is contacted against Lean Amine (J) provided OSBLvia line (21 a) to the Amine Absorber (21) to remove hydrogen sulfidefrom the gases making up the Activating Gas recycle stream (C′). Richamine (K) which has absorbed hydrogen sulfide exits the bottom of theAmine Absorber (21) and is sent OSBL via line (21 b) for amineregeneration and sulfur recovery.

The Amine Absorber overhead vapor in line (21 c) is preferably recycledto the process as a Recycle Activating Gas (C′) via the RecycleCompressor (23) and line (23 a) where it is mixed with the MakeupActivating Gas (C″) provided OSBL by line (23 b). This mixture ofRecycle Activating Gas (C′) and Makeup Activating Gas (C″) to form theActivating Gas (C) utilized in the process via line (23 c) as notedabove. A Scrubbed Purge Gas stream (H) is taken from the Amine Absorberoverhead vapor line (21 c) and sent via line (21 d) to OSBL to preventthe buildup of light hydrocarbons or other non-condensables.

Reactor System Description: The Reactor System (11) illustrated in FIG.2 comprises a single reactor vessel loaded with the process catalyst andsufficient controls, valves and sensors as one of skill in the art wouldreadily appreciate.

Alternative Reactor Systems in which more than one reactor vessel may beutilized in parallel as shown in FIG. 3a or in a cascading series asshown in FIG. 3b can easily be substituted for the single reactor vesselReactor System (11) illustrated in FIG. 2. In such and embodiment, eachof the multiple reactor vessels is in parallel and is similarly loadedwith process catalyst and can be provided the heated Feed Mixture (D′)via a common line. The effluent from each of the three reactors isrecombined in common line and forms a combined Reactor Effluent (E) forfurther processing as described above. The illustrative arrangement willallow the three reactors to carry out the process in paralleleffectively multiplying the hydraulic capacity of the overall ReactorSystem. Control valves and isolation valves may be sued to prevent feedfrom entering one reactor vessel but not another reactor vessel. In thisway one reactor can be by-passed and placed off-line for maintenance andreloading of catalyst while the remaining reactors continue to receiveheated Feedstock Mixture (D′). It will be appreciated by one of skill inthe art this arrangement of reactor vessels in parallel is not limitedin number to three, but multiple additional reactor vessels can beadded. The only limitation to the number of parallel reactor vessels isplot spacing and the ability to provide heated Feedstock Mixture (D′) toeach active reactor.

In another illustrative embodiment cascading reactor vessels are loadedwith process catalyst with the same or different activities towardmetals, sulfur or other environmental contaminates to be removed. Forexample, one reactor may be loaded with a highly active demetalingcatalyst, a second subsequent or downstream reactor may be loaded with abalanced demetaling/desulfurizing catalyst, and a third reactordownstream from the second reactor may be loaded with a highly activedesulfurization catalyst. This allows for greater control and balance inprocess conditions (temperature, pressure, space flow velocity, etc . .. ) so it is tailored for each catalyst. In this way one can optimizethe parameters in each reactor depending upon the material being fed tothat specific reactor/catalyst combination and minimize thehydrocracking reactions. As with the prior illustrative embodiment,multiple cascading series of reactors can be utilized in parallel and inthis way the benefits of such an arrangement noted above (i.e. allow oneseries to be “online” while the other series is “off line” formaintenance or allow increased plant capacity).

The reactor(s) that form the Reactor System may be fixed bed, ebulliatedbed or slurry bed or a combination of these types of reactors. Asenvisioned, fixed bed reactors are preferred as these are easier tooperate and maintain.

The reactor vessel in the Reactor System is loaded with one or moreprocess catalysts. The exact design of the process catalyst system is afunction of feedstock properties, product requirements and operatingconstraints and optimization of the process catalyst can be carried outby routine trial and error by one of ordinary skill in the art.

The process catalyst(s) comprise at least one metal selected from thegroup consisting of the metals each belonging to the groups 6, 8, 9 and10 of the Periodic Table, and more preferably a mixed transition metalcatalyst such as Ni—Mo, Co—Mo, Ni—W or Ni—Co—Mo are utilized. The metalis preferably supported on a porous inorganic oxide catalyst carrier.The porous inorganic oxide catalyst carrier is at least one carrierselected from the group consisting of alumina, alumina/boria carrier, acarrier containing metal-containing aluminosilicate, alumina/phosphoruscarrier, alumina/alkaline earth metal compound carrier, alumina/titaniacarrier and alumina/zirconia carrier. The preferred porous inorganicoxide catalyst carrier is alumina. The pore size and metal loadings onthe carrier may be systematically varied and tested with the desiredfeedstock and process conditions to optimize the properties of theProduct HMFO. Such activities are well known and routine to one of skillin the art. Catalyst in the fixed bed reactor(s) may be dense-loaded orsock-loaded.

The catalyst selection utilized within and for loading the ReactorSystem may be preferential to desulfurization by designing a catalystloading scheme that results in the Feedstock mixture first contacting acatalyst bed that with a catalyst preferential to demetalizationfollowed downstream by a bed of catalyst with mixed activity fordemetalization and desulfurization followed downstream by a catalyst bedwith high desulfurization activity. In effect the first bed with highdemetalization activity acts as a guard bed for the desulfurization bed.

The objective of the Reactor System is to treat the Feedstock HMFO atthe severity required to meet the Product HMFO specification.Demetalization, denitrogenation and hydrocarbon hydrogenation reactionsmay also occur to some extent when the process conditions are optimizedso the performance of the Reactor System achieves the required level ofdesulfurization. Hydrocracking is preferably minimized to reduce thevolume of hydrocarbons formed as by-product hydrocarbons to the process.The objective of the process is to selectively remove the environmentalcontaminates from Feedstock HMFO and minimize the formation ofunnecessary by-product hydrocarbons (C1-C8 hydrocarbons).

The process conditions in each reactor vessel will depend upon thefeedstock, the catalyst utilized and the desired final properties of theProduct HMFO desired. Variations in conditions are to be expected by oneof ordinary skill in the art and these may be determined by pilot planttesting and systematic optimization of the process. With this in mind ithas been found that the operating pressure, the indicated operatingtemperature, the ratio of the Activating Gas to Feedstock HMFO, thepartial pressure of hydrogen in the Activating Gas and the spacevelocity all are important parameters to consider. The operatingpressure of the Reactor System should be in the range of 250 psig and3000 psig, preferably between 1000 psig and 2500 psig and morepreferably between 1500 psig and 2200 psig. The indicated operatingtemperature of the Reactor System should be 500° F. to 900 F, preferablybetween 650° F. and 850° F. and more preferably between 680° F. and 800F. The ratio of the quantity of the Activating Gas to the quantity ofFeedstock HMFO should be in the range of 250 scf gas/bbl of FeedstockHMFO to 10,000 scf gas/bbl of Feedstock HMFO, preferably between 2000scf gas/bbl of Feedstock HMFO to 5000 scf gas/bbl of Feedstock HMFO andmore preferably between 2500 scf gas/bbl of Feedstock HMFO to 4500 scfgas/bbl of Feedstock HMFO. The Activating Gas should be selected frommixtures of nitrogen, hydrogen, carbon dioxide, gaseous water, andmethane, so Activating Gas has an ideal gas partial pressure of hydrogen(p_(H2)) greater than 80% of the total pressure of the Activating Gasmixture (P) and preferably wherein the Activating Gas has an ideal gaspartial pressure of hydrogen (p_(H2)) greater than 95% of the totalpressure of the Activating Gas mixture (P). The Activating Gas may havea hydrogen mole fraction in the range between 80% of the total moles ofActivating Gas mixture and more preferably wherein the Activating Gashas a hydrogen mole fraction between 80% and 99% of the total moles ofActivating Gas mixture. The liquid hourly space velocity within theReactor System should be between 0.05 oil/hour/m³ catalyst and 1.0oil/hour/m³ catalyst; preferably between 0.08 oil/hour/m³ catalyst and0.5 oil/hour/m³ catalyst and more preferably between 0.1 oil/hour/m³catalyst and 0.3 oil/hour/m³ catalyst to achieve desulfurization withproduct sulfur levels below 0.1% wt.

The hydraulic capacity rate of the Reactor System should be between 100bbl of Feedstock HMFO/day and 100,000 bbl of Feedstock HMFO/day,preferably between 1000 bbl of Feedstock HMFO/day and 60,000 bbl ofFeedstock HMFO/day, more preferably between 5,000 bbl of FeedstockHMFO/day and 45,000 bbl of Feedstock HMFO/day, and even more preferablybetween 10,000 bbl of Feedstock HMFO/day and 30,000 bbl of FeedstockHMFO/day. The desired hydraulic capacity may be achieved in a singlereactor vessel Reactor System or in a multiple reactor vessel ReactorSystem.

Oil Product Stripper System Description: The Oil Product Stripper System(19) comprises a stripper column and ancillary equipment and utilitiesrequired to remove hydrogen, hydrogen sulfide and light hydrocarbonslighter than diesel from the Product HMFO. Such systems are well knownto one of skill in the art a generalized functional description isprovided herein. Liquid from the Hot Separator (13) and Cold Separator(7) feed the Oil Product Stripper Column (19). Stripping of hydrogen andhydrogen sulfide and light hydrocarbons lighter than diesel may beachieved via a reboiler, live steam or other stripping medium. The OilProduct Stripper System (19) may be designed with an overhead systemcomprising an overhead condenser, reflux drum and reflux pump or it maybe designed without an overhead system. The conditions of the OilProduct Stripper may be optimized to control the bulk properties of theProduct HMFO, more specifically viscosity and density.

Amine Absorber System Description: The Amine Absorber System (21)comprises a gas liquid contacting column and ancillary equipment andutilities required to remove sour gas (i.e. hydrogen sulfide) from theCold Separator vapor feed so the resulting scrubbed gas can be recycledand used as Activating Gas. Such systems are well known to one of skillin the art a generalized functional description is provided herein.Vapors from the Cold Separator (17) feed the contacting column/system(19). Lean Amine (or other suitable sour gas stripping fluids orsystems) provided from OSBL is utilized to scrub the Cold Separatorvapor so hydrogen sulfide is effectively removed. The Amine AbsorberSystem (19) may be designed with a gas drying system to remove the anywater vapor entrained into the Recycle Activating Gas (C′).

The following examples will provide one skilled in the art with a morespecific illustrative embodiment for conducting the process disclosedherein:

EXAMPLE 1

Overview: The purpose of a pilot test run is to demonstrate thatfeedstock HMFO can be processed through a reactor loaded withcommercially available catalysts at specified conditions to removeenvironmental contaminates, specifically sulfur and other contaminantsfrom the HMFO to produce a product HMFO that is MARPOL compliant, thatis production of a Low Sulfur Heavy Marine Fuel Oil (LS-HMFO) orUltra-Low Sulfur Heavy Marine Fuel Oil (USL-HMFO).

Pilot Unit Set Up: The pilot unit will be set up with two 434 cm³reactors arranged in series to process the feedstock HMFO. The leadreactor will be loaded with a blend of a commercially availablehydro-demetaling (HDM) catalyst and a commercially availablehydro-transition (HDT) catalyst. One of skill in the art will appreciatethat the HDT catalyst layer may be formed and optimized using a mixtureof HDM and HDS catalysts combined with an inert material to achieve thedesired intermediate/transition activity levels. The second reactor willbe loaded with a blend of the commercially available hydro-transition(HDT) and a commercially available hydrodesulfurization (HDS).Alternatively, one can load the second reactor simply with acommercially hydrodesulfurization (HDS) catalyst. One of skill in theart will appreciate that the specific feed properties of the FeedstockHMFO may affect the proportion of HDM, HDT and HDS catalysts in thereactor system. A systematic process of testing different combinationswith the same feed will yield the optimized catalyst combination for anyfeedstock and reaction conditions. For this example, the first reactorwill be loaded with ⅔ hydro-demetaling catalyst and ⅓ hydro-transitioncatalyst. The second reactor will be loaded with allhydrodesulfurization catalyst. The catalysts in each reactor will bemixed with glass beads (approximately 50% by volume) to improve liquiddistribution and better control reactor temperature. For this pilot testrun, one should use these commercially available catalysts: HDM:Albemarle KFR 20 series or equivalent; HDT: Albemarle KFR 30 series orequivalent; HDS: Albemarle KFR 50 or KFR 70 or equivalent. Once set upof the pilot unit is complete, the catalyst can be activated bysulfiding the catalyst using dimethyldi sulfide (DMDS) in a manner wellknown to one of skill in the art.

Pilot Unit Operation: Upon completion of the activating step, the pilotunit will be ready to receive the feedstock HMFO and Activating Gasfeed. For the present example, the Activating Gas can be technical gradeor better hydrogen gas. The mixed Feedstock HMFO and Activating Gas willbe provided to the pilot plant at rates and operating conditions asspecified: Oil Feed Rate: 108.5 ml/h (space velocity=0.25/h);Hydrogen/Oil Ratio: 570 Nm3/m3 (3200 scf/bbl); Reactor Temperature: 372°C. (702° F.); Reactor Outlet Pressure:13.8 MPa(g) (2000 psig).

One of skill in the art will know that the rates and conditions may besystematically adjusted and optimized depending upon feed properties toachieve the desired product requirements. The unit will be brought to asteady state for each condition and full samples taken so analyticaltests can be completed. Material balance for each condition should beclosed before moving to the next condition.

Expected impacts on the Feedstock HMFO properties are: Sulfur Content(wt %): Reduced by at least 80%; Metals Content (wt %): Reduced by atleast 80%; MCR/Asphaltene Content (wt %): Reduced by at least 30%;Nitrogen Content (wt %): Reduced by at least 20%; C1-Naphtha Yield (wt%): Not over 3.0% and preferably not over 1.0%.

Process conditions in the Pilot Unit can be systematically adjusted asper Table 4 to assess the impact of process conditions and optimize theperformance of the process for the specific catalyst and feedstock HMFOutilized.

TABLE 4 Optimization of Process Conditions HC Feed Rate Pressure (ml/h),Nm³ H₂/m³ oil/ Temp (MPa(g)/ Case [LHSV(/h)] scf H₂/bbl oil (° C./° F.)psig) Baseline 108.5 [0.25] 570/3200 372/702 13.8/2000 T1 108.5 [0.25]570/3200 362/684 13.8/2000 T2 108.5 [0.25] 570/3200 382/720 13.8/2000 L1130.2 [0.30] 570/3200 372/702 13.8/2000 L2  86.8 [0.20] 570/3200 372/70213.8/2000 H1 108.5 [0.25] 500/2810 372/702 13.8/2000 H2 108.5 [0.25]640/3590 372/702 13.8/2000 S1  65.1 [0.15] 620/3480 385/725 15.2/2200

In this way, the conditions of the pilot unit can be optimized toachieve less than 0.5% wt. sulfur product HMFO and preferably a 0.1% wt.sulfur product HMFO. Conditions for producing ULS-HMFO (i.e. 0.1% wt.sulfur product HMFO) will be: Feedstock HMFO Feed Rate: 65.1 ml/h (spacevelocity=0.15/h); Hydrogen/Oil Ratio: 620 Nm³/m³ (3480 scf/bbl); ReactorTemperature: 385° C. (725° F.); Reactor Outlet Pressure: 15 MPa(g) (2200psig)

Table 5 summarizes the anticipated impacts on key properties of HMFO.

TABLE 5 Expected Impact of Process on Key Properties of HMFO PropertyMinimum Typical Maximum Sulfur Conversion/Removal 80% 90% 98% MetalsConversion/Removal 80% 90% 100%  MCR Reduction 30% 50% 70% AsphalteneReduction 30% 50% 70% Nitrogen Conversion 10% 30% 70% C1 through NaphthaYield 0.5%  1.0%  4.0%  Hydrogen Consumption (scf/bbl) 500 750 1500

Table 6 lists analytical tests to be carried out for thecharacterization of the Feedstock

HMFO and Product HMFO. The analytical tests include those required byISO for the Feedstock HMFO and the product HMFO to qualify and trade incommerce as ISO compliant residual marine fuels. The additionalparameters are provided so that one skilled in the art will be able tounderstand and appreciate the effectiveness of the inventive process.

TABLE 6 Analytical Tests and Testing Procedures Sulfur Content ISO 8754or ISO 14596 or ASTM D4294 Density @ 15° C. ISO 3675 or ISO 12185Kinematic Viscosity @ 50° C. ISO 3104 Pour Point, ° C. ISO 3016 FlashPoint, ° C. ISO 2719 CCAI ISO 8217, ANNEX B Ash Content ISO 6245 TotalSediment - Aged ISO 10307-2 Micro Carbon Residue, mass % ISO 10370 H2S,mg/kg IP 570 Acid Number ASTM D664 Water ISO 3733 Specific ContaminantsIP 501 or IP 470 (unless indicated otherwise) Vanadium or ISO 14597Sodium Aluminum or ISO 10478 Silicon or ISO 10478 Calcium or IP 500 Zincor IP 500 Phosphorous IP 500 Nickle Iron Distillation ASTM D7169 C:HRatio ASTM D3178 SARA Analysis ASTM D2007 Asphaltenes, wt % ASTM D6560Total Nitrogen ASTM D5762 Vent Gas Component Analysis FID GasChromatography or comparable

Table 7 contains the Feedstock HMFO analytical test results and theProduct HMFO analytical test results expected from the inventive processthat indicate the production of a LS HMFO. It will be noted by one ofskill in the art that under the conditions, the levels of hydrocarboncracking will be minimized to levels substantially lower than 10%, morepreferably less than 5% and even more preferably less than 1% of thetotal mass balance.

TABLE 7 Analytical Results Feedstock HMFO Product HMFO Sulfur Content,mass % 3.0   0.3 Density @ 15 C., kg/m³ 990 950 ⁽¹⁾ Kinematic Viscosity@ 50 C., mm²/s 380 100 ⁽¹⁾ Pour Point, C. 20 10  Flash Point, C. 110 100⁽¹⁾ CCAI 850 820  Ash Content, mass % 0.1   0.0 Total Sediment - Aged,mass % 0.1   0.0 Micro Carbon Residue, mass % 13.0   6.5 H2S, mg/kg 0 0Acid Number, mg KO/g 1   0.5 Water, vol % 0.5 0 Specific Contaminants,mg/kg Vanadium 180 20  Sodium 30 1 Aluminum 10 1 Silicon 30 3 Calcium 151 Zinc 7 1 Phosphorous 2 0 Nickle 40 5 Iron 20 2 Distillation, ° C./° F.IBP 160/320 120/248  5% wt 235/455 225/437 10% wt 290/554 270/518 30% wt410/770 370/698 50% wt  540/1004 470/878 70% wt  650/1202  580/1076 90%wt  735/1355  660/1220 FBP  820/1508  730/1346 C:H Ratio (ASTM D3178)1.2   1.3 SARA Analysis Saturates 16 22  Aromatics 50 50  Resins 28 25 Asphaltenes 6 3 Asphaltenes, wt % 6.0   2.5 Total Nitrogen, mg/kg 40003000   Note: ⁽¹⁾ It is expected that property will be adjusted to ahigher value by post process removal of light material via distillationor stripping from product HMFO.

The product HMFO produced by the inventive process will reach ULS HMFOlimits (i.e. 0.1% wt. sulfur product HMFO) by systematic variation ofthe process parameters, for example by a lower space velocity or byusing a Feedstock HMFO with a lower initial sulfur content.

EXAMPLE 2: RMG-380 HMFO

Pilot Unit Set Up: A pilot unit was set up as noted above in Example 1with the following changes: the first reactor was loaded with: as thefirst (upper) layer encountered by the feedstock 70% vol Albemarle KFR20 series hydro-demetaling catalyst and 30% vol Albemarle KFR 30 serieshydro-transition catalyst as the second (lower) layer. The secondreactor was loaded with 20% Albemarle KFR 30 series hydrotransitioncatalyst as the first (upper) layer and 80% vol hydrodesulfurizationcatalyst as the second (lower) layer. The catalyst was activated bysulfiding the catalyst with dimethyldisulfide (DMDS) in a manner wellknown to one of skill in the art.

Pilot Unit Operation: Upon completion of the activating step, the pilotunit was ready to receive the feedstock HMFO and Activating Gas feed.The Activating Gas was technical grade or better hydrogen gas. TheFeedstock HMFO was a commercially available and merchantable ISO 8217:2017 compliant HMFO, except for a high sulfur content (2.9 wt %). Themixed Feedstock HMFO and Activating Gas was provided to the pilot plantat rates and conditions as specified in Table 8 below. The conditionswere varied to optimize the level of sulfur in the product HMFOmaterial.

TABLE 8 Process Conditions Product HC Feed Temp Pressure HMFO Rate(ml/h), Nm³ H₂/m³ oil/ (° C./ (MPa(g)/ Sulfur Case [LHSV(/h)] scf H₂/bbloil ° F.) psig) % wt. Baseline 108.5 [0.25] 570/3200 371/700 13.8/20000.24 T1 108.5 [0.25] 570/3200 362/684 13.8/2000 0.53 T2 108.5 [0.25]570/3200 382/720 13.8/2000 0.15 L1 130.2 [0.30] 570/3200 372/70213.8/2000 0.53 S1  65.1 [0.15] 620/3480 385/725 15.2/2200 0.10 P1 108.5[0.25] 570/3200 371/700    /1700 0.56 T2/P1 108.5 [0.25] 570/3200382/720    /1700 0.46

Analytical data for a representative sample of the feedstock HMFO andrepresentative samples of product HMFO are provided below:

TABLE 9 Analytical Results - HMFO (RMG-380) Feedstock Product ProductSulfur Content, mass % 2.9 0.3 0.1 Density @15° C., kg/m³ 988 932 927Kinematic Viscosity @ 382 74 47 50° C., mm²/s Pour Point, ° C. −3 −12−30 Flash Point, ° C. 116 96 90 CCAI 850 812 814 Ash Content, mass %0.05 0.0 0.0 Total Sediment - Aged, 0.04 0.0 0.0 mass % Micro CarbonResidue, 11.5 3.3 4.1 mass % H2S, mg/kg 0.6 0 0 Acid Number, mg KO/g 0.30.1 >0.05 Water, vol % 0 0.0 0.0 Specific Contaminants, mg/kg Vanadium138 15 <1 Sodium 25 5 2 Aluminum 21 2 <1 Silicon 16 3 1 Calcium 6 2 <1Zinc 5 <1 <1 Phosphorous <1 2 1 Nickle 33 23 2 Iron 24 8 1 Distillation,° C./° F. IBP 178/352 168/334 161/322  5% wt 258/496 235/455 230/446 10%wt 298/569 270/518 264/507 30% wt 395/743 360/680 351/664 50% wt 517/962461/862 439/822 70% wt  633/1172  572/1062  552/1026 90% wt  >720/>1328 694/1281  679/1254 FBP  >720/>1328  >720/>1328  >720/>1328 C:H Ratio(ASTM D3178) 1.2 1.3 1.3 SARA Analysis Saturates 25.2 28.4 29.4Aromatics 50.2 61.0 62.7 Resins 18.6 6.0 5.8 Asphaltenes 6.0 4.6 2.1Asphaltenes, wt % 6.0 4.6 2.1 Total Nitrogen, mg/kg 3300 1700 1600

As noted above in Table 9, both feedstock HMFO and product HMFOexhibited observed bulk properties consistent with ISO 8217: 2017 for amerchantable residual marine fuel oil, except that the sulfur content ofthe product HMFO was significantly reduced as noted above when comparedto the feedstock HMFO.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved not only an ISO 8217:2017compliant LS HMFO (i.e. 0.5%wt. sulfur) but also an ISO 8217:2017compliant ULS HMFO limits (i.e. 0.1% wt. sulfur) product HMFO.

EXAMPLE 3: RMK-500 HMFO

The feedstock to the pilot reactor utilized in example 2 above waschanged to a commercially available and merchantable ISO 8217: 2017RMK-500 compliant HMFO, except that it has high environmentalcontaminates (i.e. sulfur (3.3 wt %)). Other bulk characteristic of theRMK-500 feedstock high sulfur HMFO are provide below:

TABLE 10 Analytical Results- Feedstock HMFO (RMK-500) Sulfur Content,mass % 3.3 Density @ 15° C., kg/m³ 1006 Kinematic Viscosity @ 50° C.,mm²/s 500

The mixed Feedstock (RMK-500) HMFO and Activating Gas was provided tothe pilot plant at rates and conditions and the resulting sulfur levelsachieved in the table below

TABLE 11 Process Conditions HC Feed Rate Nm³ H₂/ Temp Pressure Product(ml/h), m³ oil/scf (° C./ (MPa(g)/ (RMK-500) Case [LHSV(/h)] H₂/bbl oil° F.) psig) sulfur % wt. A 108.5 [0.25]  640/3600 377/710 13.8/2000 0.57B 95.5 [0.22] 640/3600 390/735 13.8/2000 0.41 C 95.5 [0.22] 640/3600390/735 11.7/1700 0.44 D 95.5 [0.22] 640/3600 393/740 10.3/1500 0.61 E95.5 [0.22] 640/3600 393/740 17.2/2500 0.37 F 95.5 [0.22] 640/3600393/740  8.3/1200 0.70 G 95.5 [0.22] 640/3600 416/780  8.3/1200

The resulting product (RMK-500) HMFO exhibited observed bulk propertiesconsistent with the feedstock (RMK-500) HMFO, except that the sulfurcontent was significantly reduced as noted in the above table.

One of skill in the art will appreciate that the above product HMFOproduced by the inventive process has achieved a LS HMFO (i.e. 0.5% wt.sulfur) product HMFO having bulk characteristics of a ISO 8217: 2017compliant RMK-500 residual fuel oil. It will also be appreciated thatthe process can be successfully carried out under non-hydrocrackingconditions (i.e. lower temperature and pressure) that substantiallyreduce the hydrocracking of the feedstock material. It should be notedthat when conditions were increased to much higher pressure (Example E)a product with a lower sulfur content was achieved, however it wasobserved that there was an increase in light hydrocarbons and wildnaphtha production.

It will be appreciated by those skilled in the art that changes could bemade to the illustrative embodiments described above without departingfrom the broad inventive concepts thereof. It is understood, therefore,that the inventive concepts disclosed are not limited to theillustrative embodiments or examples disclosed, but it is intended tocover modifications within the scope of the inventive concepts asdefined by the claims.

What is claimed is:
 1. A low sulfur heavy marine fuel oil, consistingessentially of a 100% hydroprocessed high sulfur heavy marine fuel oil,wherein prior to hydroprocessing the high sulfur heavy marine fuel oilis compliant with ISO 8217: 2017 and is of merchantable quality as aresidual marine fuel oil but a combined sulfur and Specific Contaminantsconcentration is greater than 0.5% wt., wherein the SpecificContaminates are selected from the group consisting of: vanadium,sodium, aluminum, silicon, calcium, zinc, phosphorus, nickel, iron andcombinations thereof, and wherein the low sulfur heavy marine fuel oilis compliant with ISO 8217 : 2017 and is of merchantable quality as aresidual marine fuel oil and the combined sulfur and SpecificContaminate has concentration less than 0.5 wt %.
 2. The low sulfurheavy marine fuel oil of claim 1 wherein the concentration of the sulfuris determined by ISO 14596 or ISO 8754; and wherein the concentration ofthe Specific Contaminate is determined for: vanadium by IP 501 or IP 470or ISO 14597, sodium by IP 501 or IP 470, aluminum by IP 501 or IP 470of ISO 10478, silicon by IP 501 or IP 470 of ISO 10478, calcium by IP501 or IP 470 or ISO 500, Zinc by IP 501 or IP 470 or ISO 500,phosphorous by ISO 500, nickel by IP 501 or IP 470, and iron by IP 501or IP
 470. 3. The low sulfur heavy marine fuel oil of claim 1, whereinthe high sulfur heavy marine fuel oil has a sulfur content (ISO 14596 orISO 8754) in the range from 1.0% wt. to 5.0% wt., a kinematic viscosityat 50° C. (ISO 3104) between the range from 180 mm²/s to 700 mm²/s; adensity at 15° C. (ISO 3675) between the range of 991.0 kg/m³ to 1010.0kg/m³; a CCAI is in the range of 780 to 870 ; and a flash point (ISO2719) no lower than 60.0° C.
 4. The low sulfur heavy marine fuel oil ofclaim 1, wherein the heavy marine fuel oil product has a sulfur content(ISO 14596 or ISO 8754) less than 0.5 wt %.; a kinematic viscosity at50° C. (ISO 3104) between the range from 180 mm²/s to 700 mm²/s; adensity at 15° C. (ISO 3675) between the range of 991.0 kg/m³ to 1010.0kg/m³; a CCAI is in the range of 780 to 870; a flash point (ISO 2719) nolower than 60.0° C., a total sediment—aged (ISO 10307-2) of lower than0.10% wt.; a carbon residue—micro method (ISO 10370) lower than therange of 18.00% wt. and 20.00% wt., and an aluminum plus silicon (ISO10478) content less than 60 mg/kg.
 5. A low sulfur hydrocarbon fuelcomposition consisting essentially of: a majority by volume of a 100%hydroprocessed high sulfur residual marine fuel oil and a minority byvolume of Diluent Materials, wherein prior to hydroprocessing the highsulfur heavy marine fuel oil is compliant with ISO 8217: 2017 but has acombined sulfur and Specific Contaminants concentration greater than0.5% wt. and wherein the Specific Contaminants are selected from thegroup consisting of: vanadium, sodium, aluminum, silicon, calcium, zinc,phosphorus, nickel, iron and combinations thereof, and wherein the lowsulfur heavy marine fuel composition is compliant with ISO 8217 : 2017and has a sulfur content (ISO 14596 or ISO 8754) less than 0.5 wt %; andwherein the Diluent Materials are selected from the group consisting of:hydrocarbon materials; non-hydrocarbon materials; and, solid materialsand combinations thereof.
 6. The low sulfur heavy marine fuel oil ofclaim 5 wherein the concentration of the sulfur is determined by ISO14596 or ISO 8754; and wherein the concentration of the SpecificContaminate is determined for: vanadium by IP 501 or IP 470 or ISO14597, sodium by IP 501 or IP 470, aluminum by IP 501 or IP 470 of ISO10478, silicon by IP 501 or IP 470 of ISO 10478, calcium by IP 501 or IP470 or ISO 500, Zinc by IP 501 or IP 470 or ISO 500, phosphorous by ISO500, nickel by IP 501 or IP 470, and iron by IP 501 or IP
 470. 7. Thelow sulfur heavy marine fuel oil of claim 5 wherein the concentration ofthe sulfur is determined by ISO 14596 or ISO 8754; and wherein theconcentration of the Specific Contaminate is determined for: vanadium byIP 501 or IP 470 or ISO 14597, sodium by IP 501 or IP 470, aluminum byIP 501 or IP 470 of ISO 10478, silicon by IP 501 or IP 470 of ISO 10478,calcium by IP 501 or IP 470 or ISO 500, Zinc by IP 501 or IP 470 or ISO500, phosphorous by ISO 500, nickel by IP 501 or IP 470, and iron by IP501 or IP
 470. 8. The low sulfur heavy marine fuel oil of claim 5,wherein the high sulfur heavy marine fuel oil has a sulfur content (ISO14596 or ISO 8754) in the range from 1.0% wt. to 5.0% wt., a kinematicviscosity at 50° C. (ISO 3104) between the range from 180 mm²/s to 700mm²/s; a density at 15° C. (ISO 3675) between the range of 991.0 kg/m³to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; and a flash point(ISO 2719) no lower than 60.0° C.
 9. The low sulfur heavy marine fueloil of claim 5, wherein the heavy marine fuel oil product has a sulfurcontent (ISO 14596 or ISO 8754) less than 0.5 wt %.; a kinematicviscosity at 50° C. (ISO 3104) between the range from 180 mm²/s to 700mm²/s; a density at 15° C. (ISO 3675) between the range of 991.0 kg/m³to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; a flash point(ISO 2719) no lower than 60.0° C., a total sediment—aged (ISO 10307-2)of lower than 0.10% wt.; a carbon residue—micro method (ISO 10370) lowerthan the range of 18.00% wt. and 20.00% wt., and an aluminum plussilicon (ISO 10478) content less than 60 mg/kg.
 10. A heavy marine fueloil product that is ISO 8217: 2017 compliant for a residual marine fuel,and is of merchantable quality as such, and has a sulfur content (ISO14596 or ISO 8754) less than 0.5 wt %, said product being produced by aprocess comprising: a) combining a predetermined quantity of the heavymarine fuel oil, wherein the heavy marine fuel oil has bulk propertiescompliant with ISO 8217:2017 and is merchantable as a heavy marine fueloil, but has a combined sulfur and Specific Contaminants concentrationgreater than 0.5% wt. and wherein the Specific Contaminants are selectedfrom the group consisting of: vanadium, sodium, aluminum, silicon,calcium, zinc, phosphorus, nickel, iron and combinations thereof, with apredetermined amount of an Activating Gas to form a Feedstock Mixture;b) bringing the Feedstock Mixture up to predetermined process conditionsof temperature and pressure to form a heated and pressurized FeedstockMixture; c) contacting said heated and pressurized Feedstock Mixture inat least one reactor vessel with one or more catalyst systems selectedfrom the group consisting of: an ebulliated bed supported transitionmetal heterogeneous catalyst, a fixed bed supported transition metalheterogeneous catalyst, and a combination of ebulliated bed supportedtransition metal heterogeneous catalysts and fixed bed supportedtransition metal heterogeneous catalysts, wherein said contacting takesplace under reactive process conditions to form a Process Mixture; d)removing the Process Mixture from being in contact with the one or morecatalyst systems in the at least one reactor vessel and sending theProcess Mixture via fluid communication from the at least one reactorvessel to at least one second vessel for separating the LiquidComponents of the Process Mixture from the Gaseous Components of theProcess Mixture; e) sending by fluid communication the Liquid Componentsof the Process Mixture from the at least one second vessel to at leastone third vessel, and removing from the Liquid Components of the ProcessMixture any residual gaseous components and any by-product hydrocarboncomponents to form said heavy marine fuel oil product; and, f)discharging from said at least one third vessel said heavy marine fueloil product.
 11. The product of the process of claim 10, wherein theprocess further comprises the step of blending a majority of the heavymarine fuel oil product discharged in step f with a minority of aDiluent, and wherein the Diluent Materials are selected from the groupconsisting of: hydrocarbon materials; non-hydrocarbon materials; and,solid materials and combinations thereof.
 12. The product of the processof claim 10 wherein the concentration of the sulfur is determined by ISO14596 or ISO 8754; and wherein the concentration of the SpecificContaminates is determined for: vanadium by IP 501 or IP 470 or ISO14597, sodium by IP 501 or IP 470, aluminum by IP 501 or IP 470 of ISO10478, silicon by IP 501 or IP 470 of ISO 10478, calcium by IP 501 or IP470 or ISO 500, Zinc by IP 501 or IP 470 or ISO 500, phosphorous by ISO500, nickel by IP 501 or IP 470, and iron by IP 501 or IP
 470. 13. Theproduct of the process of claim 10, wherein the high sulfur heavy marinefuel oil has a sulfur content (ISO 14596 or ISO 8754) in the range from1.0% wt. to 5.0% wt., a kinematic viscosity at 50° C. (ISO 3104) betweenthe range from 180 mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675)between the range of 991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the rangeof 780 to 870; and a flash point (ISO 2719) no lower than 60.0° C. 14.The product of the process of claim 10, wherein the heavy marine fueloil product has a sulfur content (ISO 14596 or ISO 8754) less than 0.5wt %.; a kinematic viscosity at 50° C. (ISO 3104) between the range from180 mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675) between the rangeof 991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; aflash point (ISO 2719) no lower than 60.0° C., a total sediment—aged(ISO 10307-2) of lower than 0.10% wt. ; a carbon residue—micro method(ISO 10370) lower than the range of 18.00% wt. and 20.00% wt., and analuminum plus silicon (ISO 10478) content less than 60 mg/kg.
 15. Theproduct of the process of claim 10 wherein the catalyst system comprisesa porous inorganic oxide catalyst carrier selected from the groupconsisting of alumina, alumina/boria carrier, a carrier containingmetal-containing aluminosilicate, alumina/phosphorus carrier,alumina/alkaline earth metal compound carrier, alumina/titania carrierand alumina/zirconia carrier, and a transition metal component selectedfrom the group consisting of group 6, 8, 9 and 10 of the Periodic Table.16. The product of the process of claim 10, wherein the catalyst systemcomprises one or more fixed bed supported transition metal heterogeneouscatalysts, wherein the supported transition metal heterogeneous catalystis composed of a porous alumina oxide catalyst carrier and a transitionmetal catalysts selected from the group consisting of Ni—Mo, Co—Mo,Ni—W, and Ni—Co—Mo.
 17. The product of the process of claim 10, whereinthe predetermined quantity of the Activating Gas and the predeterminedquantity of Feedstock Heavy Marine Fuel Oil is in the range of 2500 scfgas/bbl of Feedstock HMFO to 4500 scf gas/bbl of Feedstock Heavy MarineFuel Oil.
 18. The product of the process of claim 10, wherein thereactive conditions of temperature in the at least one reactor vessel isin the range between 650° F. and 850° F. and the reactive conditions ofpressure temperature in the at least one reactor vessel is in the rangebetween 1000 psig and 2500 psig; and the reactive conditions of liquidhourly space velocity in the at least one reactor vessel is in the rangebetween 0.08 oil/hour/m3 catalyst and 0.5 oil/hour/m3 catalyst.
 19. Theproduct of the process of claim 17 wherein the hydraulic capacity of theat least one reactor vessel is in range between 5,000 bbl of FeedstockHeavy Marine Fuel Oil/day and 45,000 bbl of Feedstock Heavy Marine FuelOil/day.
 20. The product of the process of claim 12, wherein the mixtureof a majority of heavy marine fuel oil product and a minority ofDiluents has a sulfur content (ISO 14596 or ISO 8754) less than 0.5 wt%.; a kinematic viscosity at 50° C. (ISO 3104) between the range from180 mm²/s to 700 mm²/s; a density at 15° C. (ISO 3675) between the rangeof 991.0 kg/m³ to 1010.0 kg/m³; a CCAI is in the range of 780 to 870; aflash point (ISO 2719) no lower than 60.0° C., a total sediment—aged(ISO 10307-2) of lower than 0.10% wt.; a carbon residue—micro method(ISO 10370) lower than the range of 18.00% wt. and 20.00% wt., and analuminum plus silicon (ISO 10478) content less than 60 mg/kg.